SYNTHETIC, STRUCTURAL, SPECTROSCOPIC AND CALCULATIONAL STUDIES OF A LITHIUM BETA-DIKETINIMATE COMPLEX

被引：21

作者：

MAIR, FS ^{[1
]}

SCULLY, D ^{[1
]}

EDWARDS, AJ ^{[1
]}

RAITHBY, PR ^{[1
]}

SNAITH, R ^{[1
]}

机构：

[1] UNIV CAMBRIDGE,CHEM LAB,CAMBRIDGE CB2 1EW,ENGLAND

来源：

POLYHEDRON | 1995年 / 14卷 / 17-18期

关键词：

D O I：

10.1016/0277-5387(95)00073-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of malonaldehyde bis(phenylimine) monohydrochloride with two equivalents of n-BuLi in the presence of hexamethylphosphoric triamide (HMPA) yielded crystals of [PhN(CH)(3)NPhLi . HMPA](2). The two LiN2C3 metallacycles of the dimeric molecule are linked by two bridging oxygens from HMPA. No spectroscopic evidence for dissociative or other equilibria was obtained. The lithium projects above the mean plane of the metallacycles. MNDO calculations on model compounds reproduced bond lengths and angles well, except that all minima were planar, ascribing the envelope conformation to a packing effect. The molecule could best be described as a 1,5-diphenyl-1,5-diazapentadienyl lithium complex, the anion having contributions from diketinimato and two equivalent keteneimine-ene-amido resonance forms. In contrast, the protonated ligand exists in a localized keteneimine-ene-amine form only.

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页码：2397 / 2401

页数：5

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